Premium
Reactions of Carbenes with Ethers: The Role of Noncovalent Interactions
Author(s) -
Mieusset JeanLuc,
Brinker Udo H.
Publication year - 2008
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200800256
Subject(s) - dichlorocarbene , chemistry , electrophile , lone pair , nucleophile , ring (chemistry) , cyclopropane , ylide , carbene , cyclopentane , medicinal chemistry , insertion reaction , bicyclic molecule , oxygen atom , stereochemistry , carbocation , photochemistry , organic chemistry , catalysis , molecule
The influence of ethers upon carbenes has been investigated computationally by the B3LYP, MP2, and MPWB1K methods. Ylide formation is only obtained with reactive‐electrophilic carbenes like cyclopentadienylidene, whereas more nucleophilic carbenes like cyclopent‐2‐enylidene associate by interactions of lone pairs of carbon and oxygen atoms with C–H bonds. Between the stabilized‐electrophilic dichlorocarbene and the oxygen lone pairs, only weak complexes are formed. Furthermore, the mechanism of the C–H insertion of dichlorocarbene into bicyclic ethers containing a three‐membered ring has been explored. The experimental data confirm the computational results. The insertion occurs easily into the α‐position of the oxygen atom in secondary ethers but not into the methyl group of methyl ethers. In all cases, insertion into the α‐position of a cyclopropane ring is not competitive.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)